Thermodynamic analysis of separating lead and antimony in chloride system

CHEN Jin-zhong()1, CAO Hua-zhen()2, LI Bo( )2,

YUAN Hai-jun()2, ZHENG Guo-qu()2, YANG Tian-zu()1
1. School of Metallurgical Science and Engineering, Central South University, Changsha 410083, China;
2. School of Chemical Engineering and Materials, Zhejiang University of Technology,
Hangzhou 310014, China
Received 13 October 2008; accepted 18 February 2009
Abstract: In chloride system, thermodynamic analysis is a useful guide to separate lead and antimony as well as to understand the
separation mechanism. An efficient and feasible way for separating lead and antimony was discussed. The relationships of
[Pb2+][Cl]2lg[Cl]T and Elg[Cl]T in Pb-Sb-Cl-H2O system were studied, and the solubilities of lead chloride at different
antimony concentrations were calculated based on principle of simultaneous equilibrium. The results show that insoluble salt PbCl2
will only exist stably in a certain concentration range of chlorine ion. This concentration range of chlorine ion expands a little with
increasing the concentration of antimony in the system while narrows as the system acidity increases. The solubility of Pb2+ in
solution decreases with increasing the concentration of antimony in the system, whereas increases with increasing the concentration
of total chlorine. The concentration range of total chlorine causing lead solubility less than 0.005 mol/L increases monotonically.
Key words: lead; antimony; separation; chloride system; thermodynamic analysis

1 Introduction
It is difficult to separate lead and antimony from
jamesonite by mineral process because they exist as
sulfide solid solutions and disseminate each other[1]. In
order to utilize comprehensively the jamesonite, it must
be treated by metallurgy method. The pyrometallurgy
process to separate the lead and antimony is described as
follows. Firstly, the lead and antimony alloy is produced
by fluidized roasting desulfurization, calcine sintering
mixture and reduction smelting in blast furnace; then, the
antimony oxide powder and crude lead are produced by
converting the lead and antimony alloy in reverberatory
furnace; finally, lead and antimony are separated. But
there are some problems in the pyrometallurgy process,
such as lots of recycle materials, long process, difficulty
in separating lead and antimony, low recovery of lead
and antimony[2].
It is easy to separate lead and antimony by using the
solubility of PbCl2 while the jamesonite is treated by
leaching in chloride system. TANG and WANG[3] used
SbCl5 as oxidant to separate the lead and antimony by
chloridization-leaching the jamesonite. The mass ratio of

lead to antimony is 3h105. WANG et al[4] used the

slurry electrolysis process to treat complex antimony
lead concentrate, and proposed that antimony can be
separated from lead in one step, and metallic antimony
can be achieved in cathode directly at the same time. The
recovery of antimony is above 98%. The lead in residue
of slurry electrolysis process is transformed into
carbonate from chloride with ammonium carbonate. The
total recoveries of lead and silver are over 95% and 80%,
respectively.
In various media, such as NaCl, HCl and CaCl2, the
solubility of PbCl2 as a function of temperature has been
studied[57]. In chloride system[89], the thermodynamic analysis of the PbCl2 solubility has been
initially studied. But the thermodynamic analysis of
PbCl2 solubility in antimony trichloride solution has not
been reported yet.
This work focused on the principle of simultaneous
equilibrium[1011] to describe the thermodynamic
details of the PbCl2 solubility in antimony trichloride
system. The feasibility and rationality of the separation
of lead and antimony in chloride system was justified in
theory and the important theory base for the study and
manufacture was also raised.

Foundation item: Project(2006BAB02B04-4-1)supported by the National Key Technology RD Program of China

Corresponding author: ZHENG Guo-qu; Tel: +86-571-88320429; E-mail: zhenggq@zjut.edu.cn
DOI: 10.1016/S1003-6326(08)60341-6

CHEN Jin-zhong, et al/Trans. Nonferrous Met. Soc. China 19(2009) 730734

2 Equilibrium equations in solution

The divalent lead ion and trivalent antimony ion can
react with chlorine ion to create a series of complex ions
in the chloride solution. The complex reactions and
equilibrium constants are shown as follows[12]:
[SbCl 3i  i ]
, i=1, 2, 3, 4, 5,6
[Sb 3  ][Cl  ]i
(1)

Sb3++iCl= SbCl 3i  i , K i

Sb3++H2O=SbO++2H+, K SbO 
Pb2++jCl= PbCl 2j  j , K j

 2

[H ] [SbO ]
3

[Sb ]

[PbCl 2j  j ]
[Pb 2 ][Cl  ] j

(2)

, j=1, 2, 3, 4

(3)
where Ki and Kj are cumulative stability constants of
complex ion at all levels. The thermodynamic data are
from Ref.[13].
We attempt to study the equilibrium in high acidity
condition, so the complex of lead and antimony with
hydroxide can be ignored. The total concentrations of
antimony, [Sb]T, lead, [Pb]T, and chlorine, [Cl]T, in the
solution can be calculated by Eqs.(4)(6):
[Sb]T

(1  K i [Cl  ]i 
i 1
4

[Pb]T

K (SbO  )
)[Sb 3  ]
[H  ]2

(4)

(1  K j [Cl  ] j )[Pb 2  ]

[Cl]T

i 1

j 1

[Cl  ]  [Pb 2  ] iK i [Cl  ]i  [Sb 3  ] jK j [Cl  ] j

where [M]T denotes the total concentration of M and [M]

is the concentration of free M.
[Sb]T, [Pb]T, [Cl]T and [H+] in Eqs.(4)(6) can be
controlled during practical work. The concentrations of
free Sb3+, Pb2+ and Cl can be calculated at the four given
values.
When the solution coexists with insoluble chloride
(PbCl2), the relationship between [Pb2+] and [Cl] is
determined by the solubility product (Ksp) of lead
chloride:
[Pb 2 ][Cl  ] 2

10 4.68

(7)

Moreover, when the solution is in a equilibrium

condition, only one electrode potential exists based on
the principle of simultaneous equilibrium: EPb 2 /Pb
EPbCl  /Pb

EPbCl 2 (s)/Pb

EPbCl  /Pb
3

0

EPbCl

/Pb

E Pb 2  /Pb

0
E Pb

2
/Pb

EPbCl 2 /Pb . The above

4

value can be calculated by the following equation:

RT
ln
nF

[Pb] T
4

(9)

1  K j [Cl ]

 j

j 1

EPbCl 2 (s)/Pb

0
EPbCl

2 (s)/Pb

RT
ln[Cl  ]
F

(10)

Then, Elg[Cl]T diagram at a given temperature

and a total lead concentration is plotted based on the
relationship between [Cl] and [Cl]T, Eq.(10). In order to
demonstrate the effect of [Sb]T, [Pb]T and [H+] on lead
electrode potential, Elg[Cl]T diagram of lead is plotted.
In Elg[Cl]T diagram, two intersection points of
the two curves are ascertained by Eqs.(9) and (10), which
are marked as and , respectively. And the range of
[Cl]T corresponding to the two points is the concentration
range of total chlorine, in which the precipitation PbCl2
exists stably.
The calculation of points and could be educed
based on the relationship among the point potentials,
EPb 2 /Pb and E PbCl 2 (s)/Pb . Also, they could be
calculated by Eq.(11) based on the principle of solubility
product:
[Pb 2  ][Cl  ]2

(6)

K sp

RT
ln[Pb 2  ]
(8)
nF
Using the total concentration of lead, [Pb]T, to take
the place of the concentration of free lead ion, [Pb2+], in
Eq.(8), Eq.(9) is formed. And the relationship between
the lead electrode potential and [Cl] at given total
concentration of lead, [Pb]T, is represented by Eq.(10):
EPb 2 /Pb

(5)

j 1

731

[Pb]T [Cl  ]2
4

1  K j [Cl ]

 j

K sp (PbCl 2 )

(11)

j 1

It is concluded that [Cl] and the corresponding

[Cl]T are gained with the help of Eq.(11) and Eq.(6),
respectively. The total chlorine concentration
corresponding to and changes as the total lead
concentration changes. So, the practical solubility curves
of solid PbCl2 at different temperatures are gained
according to [Pb]T[Cl]T diagram.

3 Thermodynamic analysis of Pb-Sb-ClH2O system

3.1 Relationship between solubility product and
lg[Cl]T at different [Sb]T
To elucidate the separating mechanism of Pb and Sb
in Pb-Sb-Cl-H2O system, the relationship between
solubility product and lg[Cl]T at different [Sb]T is firstly
studied. Fig.1 shows the curves of [Pb2+][Cl]2 vs lg[Cl]T
in Pb-Sb-Cl-H2O system at different [Sb]T. When there is
no antimony in the system, the limiting point () appears
with [Cl]T reaching a certain amount. PbCl2 precipitation

732

CHEN Jin-zhong, et al/Trans. Nonferrous Met. Soc. China 19(2009) 730734

is just observed at this point, corresponding to the value

of [Pb2+][Cl]2 in the solution larger than the solubility of
the PbCl2. However, when [Cl]T reaches the limiting
point , the precipitated PbCl2 will dissolve into the
solution again because the value of [Pb2+][Cl] in the
solution is smaller than the solubility of PbCl2. That is to
say, the insoluble salt PbCl2 will only exist stably in a
certain concentration range of the chlorine ion (between
and ). The points and move to right with
increasing antimony concentration in the system and the
concentration range of the chlorine ion expands a little as
well. The total chlorine concentration that can dissolve
the PbCl2 is about 20 mol/L, when the concentration of
antimony increases to 2.5 mol/L. However, the total
chlorine concentration is usually less than 20 mol/L in
practical antimony trichloride leaching system. Thus, the
separation of lead and antimony becomes feasible
because the insoluble salt PbCl2 will exist stably in the
certain concentration range of chlorine ion, while
antimony can be soluble in this concentration range.

Table 1 Stability constants of ions in Pb-Sb-Cl-H2O solution at

25
lg K1

lg K2

lg K3

lg K4

lg K5

lg K6

3+

Sb -Cl

2.26

3.49

4.18

4.72

4.70

4.10

2+

1.28

1.75

2.12

1.50

Complex
Pb -Cl
+

SbO

3.49

Fig.2 Elg[Cl]T diagram of Pb-Sb-Cl-H2O system at different

[Sb]T

Fig.1 [Pb2+][Cl]2 as function of lg[Cl]T in Pb-Sb-Cl-H2O

system at 25

3.2 Elg[Cl]T diagram at different [Sb]T

Fig.2 shows Elg[Cl]T diagram of Pb-Sb-Cl-H2O
system at different [Sb]T. It is clear that the equilibrium
concentration ranges of chlorine ion ascertained by
points and are similar to those in Fig.1. Moreover,
the areas in which metal lead exists stably expand with
increasing antimony concentration. The line crossing
and is linear when no antimony exists in the system
while it is curve when antimony exists in the system. The
reason may be that the Sb3+ reacts with chlorine ion more
easily than Pb2+ to create more complexes. The
difference of equilibrium constants can also be found in
Table 1. Thus, the concentration of free chlorine ion is
affected, in turn changing the areas in which metal lead
exists stably.

3.3 Elg[Cl]T diagram at different [Pb]T

To elucidate more clearly, the changes of E with
[Cl]T at different [Pb]T are studied as well. Fig.3 shows
the Elg[Cl]T diagram at different [Pb]T. The areas
ascertained by points and in which solid lead chloride
exists stably at given conditions expand a little with
increasing the total lead concentration. Point moves to
top left corner while point moves to bottom right
corner, thus the ascertained areas in which metal lead
exists stably also expand a little with increasing the total
lead concentration. Moreover, the corresponding
potentials EPb 2 /Pb and EPbCl 2n /Pb increase with
n
increasing the total lead concentration. In summary,
when the total antimony concentration and acidity of

Fig.3 Elg[Cl]T diagram of Pb-Sb-Cl-H2O system at different

[Pb]T

CHEN Jin-zhong, et al/Trans. Nonferrous Met. Soc. China 19(2009) 730734

733

system are given, [Cl]T corresponding to points and

changes with increasing the total lead concentration, as
well as changes with increasing the lead solubility in the
solution, demonstrating easy separation Sb from Pb at a
higher [Pb2+].
3.4 Elg[Cl]T diagram at different [H+]
Fig.4 shows Elg[Cl]T diagram of Pb-Sb-Cl-H2O
system at different [H+]. It can be found that point
moves to right while point stays in original place and
thus the chlorine concentration range between and
narrows with increasing the system acidity. The reason
may be that there is SbO+ in the Pb-Sb-Cl-H2O system
and it has a proportional relation with [Sb3+] and [H+].
Thus, [H+] influences [Sb3+] indirectly by influencing
[Cl] and finally the total chlorine concentration range in
which precipitated PbCl2 exists stably is also influenced.

Fig.4 Elg[Cl]T diagram of Pb-Sb-Cl-H2O system at different

[H+]

3.5 Solubility curve of PbCl2(s) at different [Sb]T

Fig.5 shows the solubility of PbCl2(s) as a function
of [Cl]T at different [Sb]T in Pb-Sb-Cl-H2O system at 25
. It is clear that the lead concentration reaches the
lowest value (0.003 5 mol/L) in solutions with [Cl]T
reaching 0.3 mol/L when there is no antimony in the
system. That is to say, when the total chlorine
concentration is less than 0.3 mol/L, the solubility of lead
decreases with increasing the total chlorine concentration.
However, when the concentration is more than 0.3 mol/L,
the solubility of lead rises sharply because increasing
chloride activity favors the formation of soluble lead
chloride complexes (PbCl i2  i , where i=1, 2, 3, 4). The
same phenomena were reported by other researchers
[1415].
The solubility of lead ion reaches the lowest value
when the total chlorine concentration is 2.0 mol/L and
the concentration of antimony in the system is 0.5 mol/L.
And the solubility of lead ion is less than 0.005 mol/L
when the total chlorine concentration ranges from 0.3

Fig.5 Solubility curve of PbCl2(s) in Pb-Sb-Cl-H2O system at

different [Sb]T

mol/L to 0.5 mol/L. The range of [Cl]T corresponding to

the solubility of lead less than 0.005 mol/L also
continually extends with the increase in total chlorine
concentration. [Cl]T range is 1.08.0 mol/L when the
concentration of antimony is 1.5 mol/L, whereas the
chlorine concentration range is 2.013.0 mol/L when the
concentration of antimony increases to 2.5 mol/L (here
two different concentrations have comparability). It is
sort well in the practical leaching system with a high
concentration of antimony. The solubility of lead
decreases with increasing the antimony concentration in
the leaching solution. So, the favorable effect on the
separation of lead and antimony is better.
Over the certain [Cl]T, the solubility of Pb upgrades
markedly with the increase in [Cl]T, but the change
tendency becomes weaker as [Sb]T increases.

4 Conclusions
1) The thermodynamic analysis of Pb-Sb-Cl-H2O
system is introduced here based on the principle of
simultaneous equilibrium.
2) The Elg[Cl]T diagram, [Pb2+][Cl]2lg[Cl]T
diagram and the solubility curves of lead chloride at
different antimony concentrations are plotted,
respectively.
3) The insoluble salt PbCl2 only exists stably in a
certain concentration range of chlorine ion. This
concentration range of chlorine ion in which insoluble
salt PbCl2 exists stably expands a little with increasing
the concentration of antimony in the system. The
solubility of Pb in solution decreases with increasing the
concentration of antimony in the system. And the
concentration range of total chlorine corresponding to
lead solubility less than 0.005 mol/L expands continually,
meaning that separating the lead and antimony is feasible.
The solubility of lead increases with the increasing of the

CHEN Jin-zhong, et al/Trans. Nonferrous Met. Soc. China 19(2009) 730734

734

concentration of total chlorine in the system, while the

concentration range of chlorine ion in which insoluble
salt PbCl2 exists stably narrows with the increasing of the
system acidity.

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(Edited by YANG Hua)